A novel of WS2–MoCuO3 supported with graphene quantum dot as counter electrode for dye-sensitized solar cells application

A novel tungsten disulfide-molybdenum copper oxide composite supported with graphene quantum dots (WM@GQDs) has been synthesized as a counter electrode (CE) for dye-sensitized solar cells (DSSCs) using a simple and low-cost ultrasonication method. The unique structure of WM@GQDs exhibits excellent power conversion efficiency due to its high catalytic activity and charge transport properties. In addition, the graphene quantum dots (GQDs) provide more active sites in the zero-dimensional materials for an I/I3− redox reaction which can improve the electrical and optical properties of the composite. The results indicate that the amount of GQDs in the composite affect the effectiveness of solar devices. When 0.9%wt of GQDs was used, the WM@GQDs composite achieved an efficiency of 10.38%, which is higher than that of the expensive platinum CE under the same conditions. The mechanism behind the improved power conversion efficiency (PCE) of the composite sample is also discussed in detail. Therefore, WM@GQDs can be an efficient material to replace platinum in DSSCs as a CE.

www.nature.com/scientificreports/ which leads to high efficiency in photoelectric transformation 6 . However, Pt is a precious metal, and its stability is insufficient, which can cause it to react with the electrolyte over time 7 . Additionally, it's high-cost limits large-scale production of DSSCs for use in household and industrial sectors. Therefore, researchers are urgently seeking alternative materials to replace Pt. Different kinds of materials, such as carbon-based materials 8 , organic polymers 9 , transition metal dichalcogenides 10 , oxide-based materials 11 , and sulfide-based materials 12 , have been investigated and have shown excellent power conversion due to their superior electrochemical properties. Graphene quantum dots (GQDs) are promising carbon-based quantum dot materials that are primarily composed of sp 2 hybridized atoms of nanometer-sized graphene sheets, giving them zero-dimensional properties 13 . GQDs have several desirable properties, including chemical inertness, biocompatibility, stable photoluminescence properties, low resistance, and good redox reversibility. In 2013, Chen et al. 14 synthesized GQDs-doped polypyrrole (PPy) as the counter electrode. The GQDs-doped PPy film has a highly porous structure and displays higher catalytic current density and lower charge transfer resistance than PPy alone toward the I 3 − /I − redox reaction. The DSSC with PPy doped with 10% GQDs showed the highest power conversion efficiency (5.27%), which is higher than that of a Pt counter electrode-based DSSC.
Recently, 2D layered transition metal dichalcogenides (TMDs) such as MoS 2 , TiS 2 , WS 2 , and MoSe 2 have been considered as potential counter electrodes (CEs) in DSSCs due to their low cost, environmentally friendly production, simple process, high electrocatalytic activity, and chemical stability 15,16 . Among these, WS 2 has received particular attention due to its thin nanosheets with a large surface area, which can increase the number of active sites on the surface and improve its activity in solar cell applications. In 2018, Yuan et al. 17 prepared MoSe 2 nanoflowers via a facile and economical hydrothermal method as CEs in DSSCs. They reported that the DSSCs assembled with MoSe 2 CEs achieved high power conversion efficiency (PCE = 7.01%) for I 3 − reduction compared to standard Pt due to their abundant active sites and stable chemical properties. However, various methods have been used to increase the electrical conductivity of TMDs, such as doping with polymers and creating composites with carbon-based and other compounds. In 2021, Silambarasan et al. 18 fabricated MoS 2 and N-doped graphene quantum dots anchored on reduced graphene oxide (rGO) through a two-step hydrothermal method for use as counter electrodes in DSSCs. The N-GQD@MoS 2 @rGO showed a photovoltaic power conversion efficiency (η) of 4.65%. This was due to the superior catalytic property of the material, which was attributed to the increased electrochemical active sites and electrical conductivity of the rGO and MoS 2 . In addition, 2D carbon materials act as a platform to reduce the agglomeration of MoS 2 and enhance the electrochemically active sites.
In this work, we synthesized a novel WS 2 -MoCuO 3 composite supported with graphene quantum dots (WM@ GQDs) through a hydrothermal method for use as a counter electrode (CE) in dye-sensitized solar cells (DSSCs). These nanocomposites were characterized in terms of their morphological and electrochemical properties using techniques such as XPS, Raman, XRD, FESEM, HRTEM analysis, and EIS. We optimized the percent weight of GQDs in the WM@GQDs composite and investigated the resulting power conversion efficiency (PCE). The 1.5% WM@GQDs composite achieved a PCE of 10.00%, which is comparable to that of the Pt standard (7.00%) due to the presence of GQDs in the composite material, which increases the rate of charge transfer processes through the electroactive layer in the WM@GQDs composite. We propose that the WM@GQDs composite could be a promising alternative CE material for DSSCs.
Prepare the WS 2 /MoCuO 3 @Graphene quantum dot CE (WM@GQDs). Graphene oxide was synthesized by Hummer's method. Graphite powder (10 g) was added to the 45 mL of concentrated sulfuric acid (H 2 SO 4 ) under continuous magnetic stirring in the ice bath. After mixing for 15 min, 2.25 g KMnO 4 was added to the solution. Then, heat the mixture solution to 50-60 °C while stirring for 2-3 h. The mixture was placed in the ultrasonic bath for 30 min at room temperature and slowly add hydrogen peroxide (H 2 O 2 ) while stirring. This step produces a strongly exothermic reaction and causes the mixture to bubble vigorously. After 2 h of stirring, the mixture is washed with deionized water to remove excess acid, nitrate, and sulfate ions. The resulting graphite oxide is dried under a vacuum to obtain a powdery substance.
The typical preparation process for graphene quantum dots (GQDs) is as follows: 500 mg of graphene oxide (GO) and 100 µL of dimethylformamide (DMF) were dissolved in 10.0 mL of deionized water under conditions of vigorous stirring. The mixture was then mixed with 3 mL of ammonia and sonicated for 20 min. Afterward, the mixture was transferred into a Teflon-lined autoclave and heated at 140 °C for 48 h 19 .
MoCuO 3 nanowires were synthesized through a hydrothermal method. 1.5 g of ammonium molybdate and 1.0 g of copper (II) oxide were dissolved in deionized (DI) water, and 5 mL of HNO 3 was added to the solution. After 10 min of stirring, the solution was transferred to a 100 mL Teflon-lined stainless steel autoclave, sealed, and placed in an air-drying oven heated at 180 °C for 12 h. The final product was rinsed with DI water until the waste solution was neutral, and the precipitate was vacuum dried.
The WS 2 powder, MoCuO 3 , and GQDs were then dispersed in DI water, stirred for 30 min, and ultrasonicated for 1 h. The uniform mixture was then transferred to a 100 mL Teflon-lined stainless-steel autoclave, centrifuged at 4000 rpm, washed with DI acetone, and dried for further use. Four concentrations of GQDs in WM@GQDs, i.e., 0.3 wt% GQDs, 0.6 wt% GQDs, and 0.9 wt% GQDs, were prepared using the same procedure. Figure 1 illustrates the method of synthesis of WM@GQDs nanocomposites. www.nature.com/scientificreports/ Fabrication of solar cell device. Typically, a fluorine-doped tin oxide (FTO) glass substrate is used to design the sandwich-type solar cell device, and the doctor blade method is used to deposit both the photo and counter electrodes 20 . First, 0.5 g of WM@GQDs is dispersed in 5 mL of ethanol and ground well for 30 min using a mortar and pestle. The slurry for each counter electrode is coated on the FTO substrate and then dried at 80 °C before being annealed at 400 °C for 2 h. The same fabrication method is followed to prepare all other photoanodes (TiO 2 , commercial P25). The N719 dye solution is immersed in the TiO 2 PE electrodes for 24 h and annealed at 400 °C for 2 h. Finally, the electrolyte solution (I − /I 3 − ) is dropped through one of the holes between the two electrodes, which are then sealed with silicon sticks to prevent evaporation.
Characterization techniques. The crystalline properties of the synthesized nanocomposites were studied using an X-ray diffractometer (SmartLab, Rigaku) under Cu Kα radiation. The morphology of the synthesized nanocomposite was investigated using field emission scanning electron microscopy (FESEM: Thermo Fisher Scientific, Apero2) and transmission electron microscopy (TEM, JEOL JEM-2100). The surface elemental composition and oxidation states were analyzed using X-ray photoelectron spectroscopy (XPS; PHI5000 VersaProbe II ULVAC-PHI, Japan) at the Synchrotron Light Research Institute (SLRI) in Thailand. Raman spectra were recorded using a microscopy Raman spectrometer (NRS-7100, JASCO). The current-voltage (I-V) characteristics of the fabricated photovoltaic devices were studied using a Class A solar simulator workstation (SL-50A-WS, SCIENCE TECH) at AM1.5 (sunlight of 100 mW/cm 2 ). For electrochemical impedance spectroscopy (EIS) measurements, the electrolyte solution consisted of 0.05 M I 2 and 0.5 M LiI in acetonitrile. Nyquist plots were recorded over a frequency range of 0.1 Hz-100 kHz and measured at 250 mV to negate the limited regime of mass transport.

Results and discussion
Characterization analysis of WM@GQDs. XRD analysis. The crystalline properties of the synthesized GQDs, WS 2 , and WM@GQDs were studied using the XRD analysis technique, as shown in Fig. 2. Analysis of the pattern recorded for GQDs reveals an amorphous structure, which is evident from the diffraction peak at 2θ = 25.8°, that corresponds to the (002) plane of the sp 2 -hybridized carbon atoms in GQDs 21   Surface morphology analysis. The surface morphology of GQDs, WS 2 , and WM@GQDs was investigated using the FESEM imaging technique, as shown in Fig. 3a-c. Figure 3a shows a monodispersed and uniform spherical structure of the prepared GQDs, with an average size of approximately 10 nm. Moreover, Fig. 3b clearly shows the presence of flake-like WS 2 nanosheets on the surface. The size of WM@GQDs ranged from 2 to 10 nm for the WS 2 -MoCuO 3 system embedded with GQDs. The microstructure of WS 2 was investigated using the highresolution TEM technique, and the results are presented in Fig. 3d-f. Figure 3d presents the HRTEM image of the GQDs, which clearly indicates the formation of stacked nanosheets. The WS 2 nanosheets were also observed  www.nature.com/scientificreports/ to agglomerate into larger clusters, as shown in Fig. 3e. The high-resolution TEM images confirm the formation of ultrathin sheets of WS 2 , GQDs, and MoCuO 3 embedded in the composite.
FTIR analysis and Raman spectra. FTIR and Raman spectroscopy were used to characterize the structure and composition of the composite. Figure 4a presented the FTIR spectral profiles recorded for GQDs, WS 2 , and WM@GQDs. The profiles recorded for GQDs present bands that confirm the graphene-like structure of the materials (the C=C backbone vibrations appear at 1921 cm −1 , and the presence of the oxygen-containing groups (such as O-H) was represented by the stretching vibrations at 3182 cm −1 . The C=O stretching vibrations appeared at 2178 cm −1 . The profiles recorded for pure WS 2 exhibits three characteristic absorption peaks at 620 cm −1 and in the region spanning 875-1051 cm −1 . These peaks were attributed to the W-S and S-S bonds in WS 2 23,24 . In addition, the spectral profiles recorded for MoCuO 3 revealed the presence of Mo-O stretching vibrations at approximately 1110 cm −1 . The band at approximately 612 cm −1 was associated with the vibrations of the O atoms in the MoCuO 3 lattice. Signals characteristic of both components were clearly observed in the spectral profiles recorded for WM@GQD.
The Raman spectra of WS 2 and WM@GQDs are presented in Fig. 5a,b to study the structure of materials and their interaction property. Figure 5a (blue line) represents the single-domain WS 2 monolayer and presents three main peaks at 1351. 76, 1577.31, 2716.15, and 32,381.12 cm −1 . The results were consistent with the reported Raman active modes of WS 2 . The three peaks corresponded to the two second-order longitudinal acoustic (LA) Raman modes at point M, E′2 g, and A1 g of WS 2 , respectively 25 . The peak at 963.72 cm −1 represented the firstorder peak of E12 g as shown in Fig. 5b. In addition, the zoomed-in peaks of WM@GQDs are shown in the  www.nature.com/scientificreports/ inset figure to confirm the composite structure (Fig. 5c). Two strong peaks were present in the spectral profiles recorded for GQDs (blue line). The G band at 1601 cm −1 indicates an ordered planar structure of the sp 2 carbon atoms (C-C bond), and the D band at 1360 cm −1 corresponds to the sp 3 structural defects (e.g., edges and functional groups). The band ratio of the peak intensity of D and G bands (I D /I G = 1.07) can reflect the participation of functional groups at the edges of the GQDs in relation to the C=C bonds in their structures.
XPS analysis. The elemental compositions, valence states, and oxidation states of the elements in the WM@ GQDs were confirmed using the X-ray photoelectron spectroscopy (XPS) technique, as shown in Fig. 6a-e. The XPS survey spectra of the WM@GQDs composite show the presence of W 4f, S 2p, Mo 3d, Cu 2p, C 1s, and O 1s in the hybrid form. There are no additional peaks in the survey spectrum, indicating the absence of impurities in the hybrid. The high-resolution spectrum of W 4f (Fig. 6b) displays a peak with a binding energy of approximately 40.8 eV, which confirms the presence of WS 2 crystals. The presence of the characteristic 2H phase (with no observable contribution from WOx) was confirmed. The S 2p profiles (Fig. 6c) exhibit the S 2p 3/2 :2p 1/2 spinorbit doublet at 164.3 and 169.1 eV, respectively, corresponding to the S 2− oxidation state expected for crystalline WS 2 26 . In addition, Fig. 6d presents the two main peaks in the Mo 3d spectrum at 232.8 and 235.7 eV, which are assigned to Mo 3d 5/2 and Mo 3d 3/2 , respectively. The C 1s spectrum (Fig. 6e) presents three peaks, corresponding to C-C/C=C at 284.8 eV, C-O at 287.1 eV, and C=O at 289.3 eV 27 . The O 1s spectrum (Fig. 6f) is divided into three sub-bands corresponding to C-O, C=O, and -OH in the GQDs. The XPS analysis confirms the presence of bonded elements present in the WM@GQD composite.
Surface area analysis. The influence of WS 2 and the WM@GQD composite was studied by analyzing the N 2 adsorption-desorption isotherms. Figure 7a,b shows that type IV isotherm adsorption curves with H3-type hysteresis loops (according to the IUPAC classification) were recorded for all the samples, indicating that mesoporous structures were formed in all samples 28 . WM@GQDs were characterized by the maximum specific surface area of approximately 69.40 m 2 /g, which was larger than that of WS 2 (25.30 m 2 /g). The pore diameter of all the samples was primarily distributed within the range of 100-200 nm, as shown in the pore size distribution curves in the inset of Fig. 7. According to the BET results, incorporating GQDs into the WM@GQDs can increase the number of active sites, which can improve the power conversion efficiency of the CEs.
Bandgap estimation. The UV-Vis spectra of the GQDs, WS 2 , and WM@GQDs are presented in Fig. 8a. The absorption region of a semiconductor is related to its band structure. The band gap energy (Eg) can be obtained from equation 29 .
As shown in Fig. 8a The higher open circuit voltage is critical for maintaining a higher driving force for electrons around the circuit so as to limit electron-hole recombinations. Moreover, the improvement of power conversion efficiency is due to the larger surface area of the WM@GQDs for I 3 − reduction 30 .
Electrocatalytic and impedance measurements analysis. The charge transfer resistance at the counter electrode-electrolyte interface has been investigated through the EIS technique. Figure 10 and Table 1 represent the Nyquist curve for the corresponding (0.3-0.9%wt) WM@GQDs and Pt electrodes with an applied frequency range of 100 MHz and 100 kHz. There are two semi-circles were obtained, the first semicircle represents the charge transfer from FTO to CEs materials and the second semicircle indicates the charge transfer of electrode and electrolyte or electrolyte resistance. From EIS spectra, the charge transfer resistance of 0.9%wt WM@GQDs (35.24 Ω) is lower when compared with 0.3%wt WM@GQDs and 0.6%wt WM@GQDs, which is due to the more electrical conductivity of graphene and high catalytic activity.
Mechanism of action of WM@GQDs. The mechanism of action of the WM@GQDs in the DSSC cell is proposed in Fig. 11. In the first step, when light falls on the photoanode side (TiO 2 absorbs N719 dyes), the photosensitive dye molecules absorb energy from sunlight. This causes the free electrons in the dye molecules to become excited and jump from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The excited electrons are then injected into the conducting layer, a conduction band of titanium www.nature.com/scientificreports/  www.nature.com/scientificreports/ dioxide, and passed on to a layer of translucent conductive glass. Numerous electrons are present in this layer, and when it is connected to an external load, an electric current is generated from the flow of electrons within the cell as they flow through the load to the cathode. This flow of electrons occurs continuously until the cycle is complete [31][32][33] .

Conclusion
A novel hybrid composite material, made of tungsten disulfide-molybdenum copper oxide supported with graphene quantum dots (WM@GQDs), was synthesized using a simple and low-cost ultrasonication method. Techniques such as X-ray diffraction analysis, field-emission scanning electron microscopy, and BET analysis were used to confirm the crystallinity and morphology of the material. When used as the 0.9% wt WM@GQDs cathode in a dye-sensitized solar cell, the material had a maximum power conversion efficiency (PCE) of 10.38%, which is higher than that of a Pt electrode (10.26%). Electrochemical impedance spectroscopy showed that the WM@GQDs material had a lower resistance compared to other cathode materials. The unique structure of the hybrid composite, with the interconnection of WS 2 -MoCuO 3 and GQDs providing a high surface area for maximal dye absorption on the electrode surface, may contribute to its high PCE.  www.nature.com/scientificreports/  www.nature.com/scientificreports/

Data availability
The datasets used and/or analysed during the current study available from the corresponding author on reasonable request.  www.nature.com/scientificreports/